Polymerization of olefins



Patented May 17, 1949 POLYMERIZATION F OLEFINS Robert M. Kennedy, Drexel Hill, and Stanford J. Hetzel, Cheltenham, Pa, assignors to Sun Oil Company, Philadelphia, Pa., a corporation of New Jersey No Drawing. Original application October 30,

1945, Serial No. 625,694. Divided and this application April 17, 1947, Serial No. 742,194

6 Claims.

This invention relates to the polymerization of normally gaseous hydrocarbons, particularly hydrocarbons having three or more carbon atoms and at least one double bond or olefinic linkage per molecule, employing a novel solid catalyst permitting the use of advantageous operating conditions, for example, materially lower pressures.

This application is a division of Serial No. 625,694, filed October 30, 1945. According to the invention normally gaseous olefins, particularly hydrocarbons having three or more carbon atoms and at least one double bond or olefinic linkage per molecule are polymerized under conditions hereinafter described in presence of a solid polymerization catalyst comprising essentially silica gel, alumina and nickel.

In one embodiment the present invention comprises a process for the polymerization of the normally gaseous olefins comprising propylene and butylenes present in hydrocarbon gases, resulting from cracking or other refinery operations, for the production of compounds, suitable for further processing into a fuel for an internal combustion or other engine, by subjecting said olefin hydrocarbons to polymerization conditions of time, temperature and pressure hereinafter described in presence of a polymerization catalyst comprising essentially silica gel, alumina and nickel.

In a further embodiment the process of themesent invention can be employed to eiiect the polymerization of other olefins, such as mono-olefins of higher molecular weight etc., in the presence or absence of propylene and butylenes or other hydrocarbon gases.

According to the invention the catalyst employed is prepared by impregnating silica gel particles, of size desired, with a water or other solution of aluminum and nickel salts. In one method of preparation solutions of aluminum and nickel nitrates of desired concentrations were added to a known quantity of silica gel, of desired particle size, in an evaporating dish. The mixture was evaporated to dryness, with stirring, and then ignited for about eight to ten hours or until the salts were completely decomposed. This was followed by reduction with hydrogen at elevated temperature.

According to the invention the catalyst composition is, by weight 80%99.98% silica gel, 0.01%-10% alumina and 0.01 %-10% nickel. Good results have been obtained with catalyst composition 90%-99% silica gel, %-5% alumina and %--5% nickel. A catalyst having a 2 composition of about 96% silica gel, about 2% alumina and about 2% nickel has been employed as will appear hereinafter.

A catalyst having an approximate composition of 98% silica gel, 1% alumina and 1% nickel was prepared by adding one liter of an aqueous solution containing 97 grams of nickel nitrate, Ni(NO3)2.6HzO, and grams of aluminum nitrate, A1(NO3)3.9H2O, to 2 kilograms of silica gel in an evaporating dish. The mixture was evaporated to dryness, with stirring, and then ignited for about nine hours to convert the nitrates to their respective oxides. Prior to use the catalyst mass was charged into a catalyst tube and ignited for one hour with air at 400 C. to ensure complete conversion to the oxides and to remove traces of water. It was then reduced with a slow stream of hydrogen for about nine hours at 400 C. to convert the nickel oxide to nickel.

While simultaneous impregnation with aluminum and nickel nitrate has been described it will be apparent to those versed in the catalyst art that other methodsfor preparation of the composition of the invention can be employed, although that described is presently preferred.

Also, for starting materials in the preparation of the catalyst composition any compound of aluminum, which upon ignition will yield alumina in activated form upon silica gel, and nickel salt, which will yield nickel oxide on ignition and which can be subsequently reduced to nickel on the silica gel can be employed, the essence of the invention insofar as it relates to the catalyst composition being in the specific combinations of materials as set forth.

For example, freshly precipitated aluminum hydroxide can be admixed with nickel hydroxide and added to silica gel and the whole ignited and then reduced as set forth previously. Or, if desired an aluminum compound and a nickel compound can be distributed on silica gel and the entire mass ignited in air followed by reduction of the ignited mass. As stated, other methods of preparation, apparent to those versed in the art can also be employed.

It is possible to substitute chromia for the alumina, and cobalt for the nickel in the catalyst composition.

It appears that advantageous results canbe obtained when employing a composition containing less alumina than nickel. While the quantity of alumina should be substantially smaller than that of nickel it is absolutely necessary that an appreciable quantity of alumina be present.

The period of activity of the catalyst will naturally vary with circumstances of its use. In the polymerization of olefinic hydrocarbons, tests have shown that a practical conversion can be obtained for periods up to hours without reupon whether these gases are to be polymerized separately or in combination with each other in the presence or absence of other hydrocarbons. If substantially pure propylene is to be converted n r n- The cataly :C be r n ra 5- a temperature. in. the range of 300,C.-400 C., many timesto. substantially it original. activity; preferablyiabout 325 C.-375" C.';' can be employed. After seventy-five regenerations, tests have If normal butylene is to be polymerized a temshown that the activity was essentially unperature in the range of 250 (3,400 c prefchanged. erably 275 C.-325 C., can be employed. If iso- In copending application Serial No. 625,692, -'-10 butyleneis to be separately polymerized a temfiled October 30, 1945, by the instant invent0rs,:-. Y pel'ature withimthe range of 200 3,400 0,, there is described and claimed afcatalyst compo. preferably 25 0 C.-300 CI, can be employed. sition consisting by weight of 80%-99.-98%- .-si1ica If the foregoing, gases ar t be polymerized 0.01% alumina or chromia and 0.01 together a temperature. within the range of 200 10% nickel or cobalt. 5 C.40Q.C., preferably250 C.-350 C., can be em- Also, in copending application Serial? No. played-,

625,693, filed October 30, 1945;"now .Pate'nt', It is tobe. understood that temperatures out- 2,452,190, by the instant inventors, there is deside these ranges are not excluded from the scribed and claimed a process for the polymrizal scope of theinvention.

tion of a compound containing two or more car- The pressure employed for the polymerization boniatoms. and a=doub1e bond .per molecule emof propylene and the butylenes will depend upon p y ia catalyst consisting ess n lly ofsilica whether theseare to be polymerizedseparately gel, alumina and nickel orcobaltu or in combination with each other in the presence In copendingapplication Serial. ;No. 525,694,: or absence of otherhydrocarbons. .If substanfiled byus October 30,"1945, upon whichiissuedtzs tially pure propylene .is to beiconverteda'pres- Patent'No. 2,452,198,1on October- 26; 1948, there sure inthe range 30=lbs./sq.,in.-150 lbs/sq. ,in.., is described a process for polymerizingzolefins' :1; preferably in the range 50 -lbs./sq. in.-100 lbs./sq.; utilizing silica-gel, aluminaga'ndia metal selected in., can be employed. If normal butylene is to. from the group of nickel and .cobalt; and there be polymerized a pressurein the range 30 lbs/sq. is also describedbut notclaimedzthe 'subject3o in.-250 lbs/sq. in., preferably in the rangegfiO; matter claimed herein, namely the utilization. lbs/sq. .in.150 lbs/sq. in., can beemployednglf of silica gel, chromia and nickel or cobalt... isobu-tylene is to be separately. polymerizedga:

As stated, the process of'the presentxinvention pressure within the range .30 lbs/sq. ins-250 is applicable to the polymerization of olefins such lbs/sq. in., preferably 60' lbs/sq. in.-l00 lbs'./.sq. 1 as propylene, the butylenesand'otherLhydroin., can be employed. carbons. If the foregoing gases-are to be polymerized;

According to the invention the hydrocarbon 1 together a pressure in the range.30;lbs./,sq. in.', 7 to be polymerizedis c'o'ntacted-With'-the catalyst 1 250 lbs/sq. in., preferably in the range .6 0 .lbs-,/,sq. in suitable apparatus under conditions-of-contact in.150 lbs/sq. in., can be employed. 1 time, temperature'and pressure described herein It is. to be understood that pressures .outside after. the foregoing pressure ranges can be employed When polymerizing propylene and 'butylenes; 4 but these are not, at present,-preffi1red.. Presor other gases, the charging rate, or timeof 'cona 5 sures from about atmospheric pressuretoabout I tact, will preferablybe such' as to allowfthese 1,000 lbs/sq. in. are not excludedifrom the scope. gases to remain incontactwith the catalyst 'for 5 of the invention. a time sufficient to c'ausethe desired degree f of The following table shows=resultsobtained ac conversion. Charging rates on gram- 12 grams cording to the invention. 5

Catalyst Composition, Weight Yield, Weight Per Cent Per Cent 1 I Pressure, 4 Unreacted,

Silica gel Alumina Nickel 3:2 recycle I ag rebycle 94.6 1 4.5 .0250 .400 9.0 16.4 6.1 12.2 55. 94.5 1 4.5 .0120 .400 60 12.2 36.1 3.1 25.1 66. 9s 1 1 .0622 -300 60 24.3 1 61.9 5 13.3 -34.0 60. 96 2 2 .0510 1 :300 60 14.5 63.3 1.4 32.2 11. 5 5 .0432 00 60 9.5 41.5 8.0 40.0 80. 90 5 5 .0390 -300 60 1.1 31.4 10.1 56.3 81. 94.5 1.0 4.5 .0310 1 300 60 21.8 50.2 14.5 33.3 56. 93.0 1.0 1.0 .0828 300 250 35.0 31.5 51. 94.5 1.0 4.5 ISObulJGDEi .1210 -300 200 19.0 82.5 11.

1 Grams gas/minJgram catalyst. gas/per minute/per 100 gramsof catalyst have A distinct advantage-of the .invent'iomis.that..."- been employed. It is, however; within the scope certain compounds :not heretofore: polymerizabl of the invention to employ lower or higher 'charg-' v to a substantialextent can be .polyme'rizedgin goo ing rates with or without recycling of any in yield. For examplaithas beeniound unexpect. completely reacted gases. For example; incom j edly,. that alpha and beta. biityleneszirtthe ab pletely reacted or unreacted gases can be treated 1 1 sence of isobutylene can be substantiallyi-poly. in subsequent zones wherein an identical catalyst merized. .The prior art yield .has beenrdue large The temperature employed for the p'olymeriza tion of propylene and the butylenes willde'pen'd ly to the polymerization. of.isobutylenetortosthe polymerization of alpha and beta 'butylenes'in the. .1; r

' presenceof'isobutylenes;.

'I'he polymerization "of the gasesjaccording to- "-7 this'in'ventionc'an be effected employing 'recy cling of any unreacted gases. A series of conversion or polymerization zones can be employed in series or in parallel. Each zone may be alternately used to polymerize gases or for the regeneration of the catalyst therein. The catalyst may be circulated through the polymerization zone, or zones, according to methods within the skill of those versed in the art.

Various modifications within the scope of the invention as defined herein and in the claims will be obvious to those skilled in the art.

We claim:

1. A process for the polymerization of olefins containing three or more carbon atoms per molecule which comprises contacting the olefins under polymerizing conditions with a catalyst consisting by weight of 80%99.98% silica gel, 0.01 chromia and 0.01%10% of a metal selected from the group consisting of nickel and cobalt.

2. A process for the polymerization of propylene which comprises contacting propylene at a temperature within 300 C.-400 C. and at a pressure within 30 lbs/sq. in.150 lbs./sq. in. with a catalyst consisting by weight of 80%-99.98% silica gel, 0.01-10% chromia and 0.01%10% nickel.

3. A process for the polymerization of n-butylene which comprises contacting n-butylene at a temperature within 250 C.-400 C. and at a pressure within 30 lbs/sq. in.-250 lbs/sq. in. with a catalyst consisting by weight of 80%-99.98% silica gel, 0.01%10% chromia and 0.01%10% nickel.

4. A process for the polymerization of i-butylene which comprises contacting i-butylene at a temperature within 200 c.-4oo c. and at a 35 2,332,276

pressure within 30 lbs./ sq. in.-250 lbs. sq. in. with a catalyst consisting by weight of 80%-99.98%

and a compound of the group consisting of nickel and cobalt, which will yield the oxide on ignition, igniting the mass "and then reducing the ignited mass.

6. A process for the polymerization of olefins containing three and four carbon atoms per molecule which comprises contacting the olefins at a temperature within the range 200 C.-400 C. with a catalyst consisting by weight of 99% silica gel, /2%5% chromia and /2%-5% nickel, said catalyst having been prepared by adding chromium and nickel nitrates in aqueous solution to silica gel, evaporating and igniting the masses and then reducing the ignited mass.

ROBERT M. KENNEDY. STANFORD J. HETZEL.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date Stahly Oct. 19, 1943 2,380,358 Anderson et al July 10, 1945 2,381,198 Bailey et al. Aug. 7, 1945 

